Thiourethane-based optical material

专利摘要:
Provided is a method of obtaining a high refractive index resin having excellent physical properties such as transparency, color, heat resistance, and impact resistance. A polythiol compound having a dithioacetal, dithioketal, orthotrithioformate ester or orthotetrathiocarbonate ester skeleton, having two or more mercapto groups, and a compound having two or more iso (thio) cyanato groups As a composition to contain, the polymeric composition for high refractive index resins whose molar ratio of a mercapto group and an iso (thio) cyanato group is more than 1.0 and 3.0 or less, the manufacturing method of resin obtained by hardening this composition, and resin obtained by hardening the composition And the optical element which consists of this resin, and the lens which consists of an optical element are provided.
公开号:KR20040053258A
申请号:KR10-2004-7006669
申请日:2003-04-16
公开日:2004-06-23
发明作者:다나까마모루；구마시게또시；후나야무네히또；고바야시세이이찌
申请人:미쓰이 가가쿠 가부시키가이샤；
IPC主号:

专利说明:

Thiurethane-based optical material {THIOURETHANE-BASED OPTICAL MATERIAL}
[2] Plastic lenses are rapidly spreading to optical elements such as spectacle lenses and camera lenses because they are lighter than inorganic lenses and can be dyed without being easily broken. Higher performance is required for resins for plastic lenses, and high refractive index, high Abbe number, low specific gravity and high heat resistance have been required. Until now, various resin materials for lenses have been developed and used. As a typical example, there is a plastic lens made of a polythiourethane resin (Japanese Patent Laid-Open No. 60-199016, Japanese Patent Laid-Open No. 62-267316, Japanese Patent Laid-Open No. 63-46213). In addition, a polythiourethane resin having a higher refractive index has been developed by increasing the sulfur content of thiol used in polythiourethane (Japanese Patent Application Laid-Open No. Hei 2-270859 and Japanese Laid-Open Patent Application Hei 7-252207).
[3] According to these methods, a high refractive index can be realized while having a relatively high Abbe number, but in order to obtain a polyurethane resin having a higher refractive index, it is necessary to develop new high sulfur-containing thiols or high sulfur-containing polyisocyanates. . However, the development of these new compounds is not easy. In addition, when used as an optical element such as a plastic lens resin, high performance is required even for physical properties other than refractive index such as transparency, color, heat resistance, and impact resistance. Therefore, a urethane resin having a higher refractive index that satisfies these various requirements is required. It is very difficult to develop.
[4] Conventionally, when a thiourethane resin is produced by polymerization of polythiol and polyiso (thio) cyanate, it is common to prepare a polymerizable composition such that the molar ratio of mercapto group and iso (thio) cyanato group is 1. Few examples examined in detail the molar ratio and the physical properties of the resin. This results in a significant decrease in the heat resistance of the resin obtained by polymerization when the molar ratio is made larger than 1 using a conventional polythiol compound, that is, when the mercapto group is excessive with respect to the iso (thio) cyanato group, thereby reducing the plastic lens or the like. This is because it may not be practically used as an optical element. However, in general, a compound having a high sulfur content tends to have a high refractive index, so that a polythiol compound is often higher in refractive index than a polyiso (thio) cyanate. For this reason, when a thiurethane resin can be manufactured using the polythiol which is a high refractive index compared with polyiso (thio) cyanate excessively, high refractive index of a resin becomes possible.
[5] Therefore, it is an object of the present invention to provide a method of easily obtaining a high refractive index resin.
[1] The present invention relates to resins used in optical materials such as plastic lenses, prisms, optical fibers, information recording plates, filters, and light emitting diodes, and to polymerizable compositions and polymerizable compositions used as raw materials for the resins. In particular, it is used suitably for the spectacle lens which has a high refractive index.
[6] MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve the above-mentioned subject, and, as a result, using the polythiol compound which has dithioacetal, dithio ketal, ortho trithio formate ester, or ortho tetrathio carbonate ester frame | skeleton in a molecule | numerator. It has been found that the above problems can be overcome. That is, in the polymerizable composition containing the polythiol compound and polyiso (thio) cyanate compound which have a dithio acetal, a dithio ketal, an ortho trithio formate ester, or an ortho tetrathio carbonate ester frame | skeleton in a molecule | numerator, By curing the polymerizable composition in which the molar ratio of the iso (thio) cyanato group is greater than 1.0, that is, the mercapto group is excessive with respect to the iso (thio) cyanato group, the lowering of the heat resistance is suppressed to a minimum. It has been found that a resin having a high refractive index can be obtained, and the present invention has been completed.
[7] That is, this invention consists of the following structures.
[8] [1] a polythiol compound having a dithioacetal, dithioketal, orthotrithioformate ester or orthotetrathiocarbonate ester skeleton and having two or more mercapto groups, and two or more iso (thio) cyanato groups The composition containing the compound which has, The polymer composition for high refractive index resins whose molar ratio of a mercapto group and an iso (thio) cyanato group is more than 1.0 and 3.0 or less.
[9] [2] The polymerizable composition according to (1), wherein the polythiol compound has a mercaptomethylthio group.
[10] [3] The polymerizable composition according to [1] or [2], containing a polythiol compound having a dithioacetal or dithioketal skeleton represented by the following General Formula (1):
[11]
[12] (Wherein R ¹ is an n-valent aliphatic residue, a heterocyclic residue, an aromatic residue, R ² is a hydrogen atom or a monovalent aliphatic residue, a heterocyclic residue, an aromatic residue, and R ³ and R ⁴ are each independently monovalent An aliphatic moiety, a heterocyclic moiety, or an aromatic moiety, wherein R ³ and R ⁴ may combine to form a ring, and when n is 2 or more, may combine with R ³ or R ⁴ in other parentheses to form a ring; Provided that at least one of R ¹ , R ² , R ^3, and R ⁴ has at least one mercapto group, and that the number of mercapto groups in R ¹ , R ² , R ^3, and R ⁴ has m1, When m2, m3 and m4 are set, m1 + (m2 + m3 + m4) × n ≧ 2; n represents an integer of 1 or more.).
[13] [4] The polymerizable composition according to [3], wherein R ² in General Formula (1) is a hydrogen atom.
[14] [5] polythiol compounds having a dithioacetal skeleton include 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, At least one polythiol selected from 4,6-bis (mercaptomethylthio) -1,3-dithiane and 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-diethane The polymerizable composition as described in (4) which is a compound.
[15] [6] The polymerizable composition according to [1] or [2], which contains a polythiol compound having an orthotrithioformate ester skeleton represented by the following General Formula (2):
[16]
[17] (Wherein R ⁵ represents p-valent aliphatic residue, heterocyclic residue, aromatic residue, R ⁶ and R ⁷ each independently represents monovalent aliphatic residue, heterocyclic residue, aromatic residue, and R ⁶ and R ⁷ are bonded) Wherein at least one of R ⁵ , R ^6, and R ⁷ has at least one mercapto group, and m 5 represents the number of mercapto groups each of R ⁵ , R ^6, and R ⁷ has; , m6 and m7, m5 + (m6 + m7) × p ≧ 2; p represents an integer of 1 or more.).
[18] [7] The polymerizable composition according to [6], wherein R ⁶ and R ⁷ in General Formula (2) are mercaptomethyl groups.
[19] [8] The polythiol compound represented by the general formula (2) is tris (mercaptomethylthio) methane, 1,1,5,5-tetrakis (mercaptomethylthio) -2,4-dithiapentane And bis (4,4-bis (mercaptomethylthio) -1,3-dithiabutyl) (mercaptomethylthio) methane, the polymerizable composition as described in [7] being one or more polythiol compounds selected from methane.
[20] [9] The polymerizable composition as set forth in [1] or [2], which contains a polythiol compound having an orthotetrathiocarbonate ester skeleton represented by the following General Formula (3):
[21]
[22] (Wherein R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent an aliphatic moiety, a heterocyclic moiety, an aromatic moiety, and each may combine with another group to form a ring; provided that R ⁸ , At least one of R ⁹ , R ¹⁰ and R ¹¹ has at least one mercapto group, and the number of mercapto groups in R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ is m8, m9, m10 and m11, respectively. M8 + m9 + m10 + m11 ≥ 2).
[23] [10] A method for producing a resin obtained by curing the polymerizable composition according to any one of [1] to [9].
[24] [11] A resin obtained by curing the polymerizable composition according to [1] to [9].
[25] [12] An optical element comprising the resin according to [11].
[26] [13] A lens comprising the optical element according to [12].
[27] [14] 4,6-bis (mercaptomethylthio) -1,3-dithiane.
[28] [15] 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-diethane.
[29] Best Mode for Carrying Out the Invention
[30] EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
[31] In the present invention, the excess ratio of the polythiol compound is appropriately determined, but the polythiol and the polyiso (thio) cyanate are prepared so that the molar ratio of the mercapto group and the iso (thio) cyanato group is greater than 1.0 and not more than 3.0 and polymerized. It is set as a sex composition.
[32] The polymerizable composition of the present invention is characterized in that the mercapto group is excessive with respect to the iso (thio) cyanato group in the composition. That is, by making molar ratio (SH / NCO) of a mercapto group and an isocyanato group larger than 1.0, it becomes possible to obtain resin which has a high refractive index compared with the case where molar ratio is 1.0. On the other hand, although the upper limit of molar ratio changes with heat resistance of resin hardened | cured by molar ratio 1.0, when 3.0 or less, the heat resistance of hardened | cured material can be kept high.
[33] The molar ratio of the mercapto group and the isocyanato group in the present invention is 1.0 <(SH / NCO) ≦ 3.0, preferably 1.01 <(SH / NCO) ≦ 3.0, more preferably 1.01 <(SH / NCO) ≤ 2.0, most preferably 1.05 <(SH / NCO) ≤ 1.3.
[34] The polythiol compound of this invention is a polythiol compound which has dithioacetal, dithio ketal, ortho trithio formic acid ester, or ortho tetrathio carbonate ester frame | skeleton. Although there will be no restriction | limiting in particular if it is polythiol which has these frame | skeleton, The polythiol which has a dithioacetal or a dithio ketal skeleton can be represented by following General formula (1), for example.
[35]
[36] Wherein R ¹ is an n-valent aliphatic residue, a heterocyclic residue, an aromatic residue, R ² is a hydrogen atom or a monovalent aliphatic residue, a heterocyclic residue, an aromatic residue, and R ³ and R ⁴ are each independently monovalent aliphatic And a residue, a heterocyclic residue, and an aromatic residue. R ³ and R ⁴ may be bonded to each other to form a ring. When n is 2 or more, it may be bonded to R ³ or R ⁴ in other parentheses to form a ring. Provided that at least one of R ¹ , R ² , R ^3, and R ⁴ has at least one mercapto group, and that the number of mercapto groups of R ¹ , R ² , R ^3, and R ⁴ is m1 and m2, respectively. , m3 and m4, m1 + (m2 + m3 + m4) × n ≧ 2. n represents an integer of 1 or more.
[37] R ¹ is not particularly limited as long as it is an n-valent organic residue derived from aliphatic, heterocyclic, or aromatic, but preferably has 1 to 15 carbon atoms. For example, n-valent organic residues derived from linear aliphatics such as methane, ethane, propane, butane, pentane, hexane, ethylene, propylene, 1-butene, 2-butene, butadiene, cyclopentane, cyclopentene, cyclopenta Dienes, cyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, cyclohexene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, norbornene N-valent derivatives derived from cyclic aliphatics such as phosphorus (norbornane), 2,3-dimethyl norbornene, 2,5-dimethyl norbornene, 2,6-dimethyl norbornene, and bis (4-methylcyclohexyl) methane Organic residue, thiolane, 2,5-dimethylthiolane, 3,4-dimethylthiolane, 2,3-dimethylthiolane, 2,4-dimethylthiolane, 2,5-diethylthiolane, 3,4-diethylthiolane, 2 , 3-diethylthiolane, 1,3-dithiolene, 2,4-dimethyl-1,3-dithiolene, 4,5-dimethyl-1,3-dithiene, 2,4-diethyl-1,3 -Dithiolene, 4,5-diethyl-1,3-dithiolene, 1,3-dithiolane, 2,4- Dimethyl-1,3-dithiolane, 4,5-dimethyl-1,3-dithiolane, 2,4-diethyl-1,3-dithiolane, 4,5-diethyl-1,3-dithiolane, Thiophene, 2,5-dimethylthiophene, 1,4-dithiane, 2,5-dimethyl-1,4-dithiane, 2,6-dimethyl-1,4-dithiane, 2,3-dimethyl- 1,4-dithiane, 2,5-diethyl-1,4-dithiane, 2,6-diethyl-1,4-dithiane, 2,3-diethyl-1,4-dithiane, 1 , 3,5-tritriane, 2,4-dimethyl-1,3,5-tritriane, 2,4-diethyl-1,3,5-tritriane, thiazole, 1,3,4-thiadia N-valent organic residues derived from heterocycles such as sol, 1,3-diethane, 2,4-dimethyl-1,3-dithiethane, 2,4-diethyl-1,3-dithiethane,
[38] Mercap from n-valent organic residues derived from aromatics such as benzene, o-xylene, m-xylene, p-xylene, naphthalene, biphenyl, anthracene, perylene, styrene, ethylbenzene, and known thiol compounds And n-valent organic residues formed by removing the earthenware.
[39] As a known thiol compound, for example, monofunctional thiols such as methanethiol, ethanethiol, 2-mercaptoethyl-1,3-dithiane, thiophenol, benzylthiol, methanedithiol and 1,2-ethanedithi Ol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetri Thiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2 -Methylcyclohexane-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, thiomalic acid bis (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2 Mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptopropionate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropio) Nate), 1,2-dimercaptopropylmethylether, 2,3-dimercaptopropylmethylether, 2,2-bis (mer) Captomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropanebis (2-mercaptoacetate), trimethylolpropanebis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), tetrakis Aliphatic polythiol compounds such as (mercaptomethyl) methane,
[40] 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene , 1,4-bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1 , 2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2, 4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) Benzene, 1,3,5-tris (mercaptoethyl) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di (p-methoxyphenyl) propane-2,2- Aromatic polythiols such as dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane,
[41] 1,2-bis (mercaptoethylthio) benzene, 1,3-bis (mercaptoethylthio) benzene, 1,4-bis (mercaptoethylthio) benzene, 1,2,3-tris (mercaptomethyl Thio) benzene, 1,2,4-tris (mercaptomethylthio) benzene, 1,3,5-tris (mercaptomethylthio) benzene, 1,2,3-tris (mercaptoethylthio) benzene, 1 Aromatic polythiol compounds containing sulfur atoms in addition to mercapto groups such as 2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, and nucleoalkylates thereof ,
[42] Bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethyl Thio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2-bis (2-mercaptoethyl Thio) ethane, 1,2-bis (3-mercaptopropyl) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3- Bis (3-mercaptopropylthio) propane, 1,2,3-tris (mercaptomethylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, 4,8-dimercaptomethyl-1,11-mercapto-3, 6,9-trithiaoundecan, 4,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaoundecan, 5,7-dimercaptome -1,11-mercapto-3,6,9-trithiaoundecan, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercapto Propylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, bis (1,3-dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane, 2 , 5-dimercaptomethyl-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, bis (mercaptomethyl) disulfide, bis (mercapto Ethyl) disulfide, bis (mercaptopropyl) disulfide and the like, and esters of thioglycolic acid and mercaptopropionic acid,
[43] Hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mer Captoacetate), hydroxymethyldisulfidebis (3-mercaptopropionate), hydroxyethyldisulfidebis (2-mercaptoacetate), hydroxyethyldisulfidebis (3-mercaptopropionate), Hydroxypropyl disulfide bis (2-mercaptoacetate), hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl etherbis (2-mercaptoacetate), 2-mercaptoethyl Etherbis (3-mercaptopropionate), 1,4-dithiane-2,5-diolbis (2-mercaptoacetate), 1,4-dithiane-2,5-diolbis (3-mercaptopropionate), thiodiglycol bis ( 2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), 4,4-thiodibutyl acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl Ester), dithiodipropionate bis (2-mercaptoethyl ester), 4,4-dithiodibutyl acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester) , Thiodipropionic acid bis (2,3-dimercaptopropyl ester), dithioglycolic acid bis (2,3-dimercaptopropyl ester), dithiodipropionic acid bis (2,3-dimercaptopropyl ester), etc. Aliphatic polythiol compounds containing sulfur atoms in addition to the mercapto group of
[44] Heterocyclic compounds containing sulfur atoms in addition to mercapto groups such as 3,4-thiophendithiol, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercaptoethanol, 3-mercapto- 1,2-propanediol, glycerindi (mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 3 , 4-dimercapto-2-propanol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, penta Erythritol tris (3-mercaptopropionate), pentaerythritol mono (3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycorate), dipentaerythritol Methacrylates such as pentacis (3-mercaptopropionate), hydroxymethyl-tris (mercaptoethylthiomethyl) methane, and 1-hydroxyethylthio-3-mercaptoethylthiobenzene The compound containing a hydroxyl group other than a lecapto group is mentioned.
[45] As monovalent aliphatic residue, heterocyclic residue, or aromatic residue in R <^2> , R <^3> and R <^4> , Monovalent organic residue derived from linear aliphatic, cyclic aliphatic, a heterocyclic ring, aromatic illustrated in R <^1> , or The organic residue formed by removing one mercapto group from the said thiol compound is mentioned. Moreover, when R <^3> and R <^4> combine and form a ring, it is a 4-8 membered ring, for example, 1, 3- dithiacyclo butane, 1, ^3- dithiacyclo as a ring containing a dithioacetal structure. Pentane, 1,3-dithiacyclohexane, 1,3-dithiacycloheptane, and the like. In addition, when n is 2 or more, 4,6-bis (mercaptomethylthio) -1,3-dithiacyclohexane which is an exemplary compound mentioned later which R <^3> in the other parentheses couple | bonds and forms a ring when n is two or more. And the like.
[46] There is no restriction | limiting in particular if n is an integer greater than or equal to 1, However, since n may become complicated to refine | purify and handling, it is preferable that it is an integer of 1-4.
[47] More specifically, the compound represented by the formula (1) is 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane , 4,6-bis (mercaptomethylthio) -1,3-dithiacyclohexane, 1,1,5,5-tetrakis (mercaptomethylthio) -3-thiapentane, 1,1,6, 6-tetrakis (mercaptomethylthio) -3,4-dithiahexane, 2,2-bis (mercaptomethylthio) ethanethiol, 2- (4,5-dimercapto-2-thiapentyl)- 1,3-dithiacyclopentane, 2,2-bis (mercaptomethyl) -1,3-dithiacyclopentane, 2,5-bis (4,4-bis (mercaptomethylthio) -2-thia Butyl) -1,4-dithiane, 2,2-bis (mercaptomethylthio) -1,3-propanedithiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-di Thiaheptane, 3,6-bis (mercaptomethylthio) -1,9-dimercapto-2,5,8-trithianonane, 4,6-bis (mercaptomethylthio) -1,9-di Mercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-diti Hexane, 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithiethane, 1,1,9,9-tetrakis (mercaptomethylthio) -5- (3,3- Bis (mercaptomethylthio) -1-thiapropyl) 3,7-dithianonane, tris (2,2-bis (mercaptomethylthio) ethyl) methane, tris (4,4-bis (mercaptomethylthio) ) -2-thiabutyl) methane, tetrakis (2,2-bis (mercaptomethylthio) ethyl) methane, tetrakis (4,4-bis (mercaptomethylthio) -2-thiabutyl) methane, 3 , 5,9,11-tetrakis (mercaptomethylthio) -1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexa Keith (mercaptomethylthio) -1,19-dimercapto-2,6,8,12,14,18-hexathianonadecane, 9- (2,2-bis (mercaptomethylthio) ethyl)- 3,5,13,15-tetrakis (mercaptomethylthio) -1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,4,8,9- Tetrakis (mercaptomethylthio) -1,11-dimercapto-2,5,7,10-tetrathiaoundecan, 3,4,8,9,13,14-hexakis ( Lecaptomethylthio) -1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane, 8- {bis (mercaptomethylthio) methyl} -3,4,12, 13-tetrakis (mercaptomethylthio) -1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4,6-bis {3,5-bis (mercapto Methylthio) -7-mercapto-2,6-dithiaheptylthio} -1,3-dithiane, 4- {3,5-bis (mercaptomethylthio) -7-mercapto-2,6- Dithiaheptylthio} -6-mercaptomethylthio-1,3-dithiane, 1,1-bis {4- (6-mercaptomethylthio) -1,3-ditianylthio} -3,3- Bis (mercaptomethylthio) propane, 1,3-bis {4- (6-mercaptomethylthio) -1,3-ditianylthio} -1,3-bis (mercaptomethylthio) propane, 1- {4- (6-mercaptomethylthio) -1,3-dithiaylthio} -3- {2,2-bis (mercaptomethylthio) ethyl} -7,9-bis (mercaptomethylthio)- 2,4,6,10-tetrathiaoundecan, 1- {4- (6-mercaptomethylthio) -1,3-ditianylthio} -3- {2- (1,3-dithiethanyl) } Methyl-7,9-bis (mercaptomethyl tee ) -2,4,6,10-tetrathiauntecan, 1,5-bis {4- (6-mercaptomethylthio) -1,3-ditianylthio} -3- {2- (1,3 -Dithiethanyl)} methyl-2,4-dithiapentane, 4,6-bis [3- {2- (1,3-dithiethanyl)} methyl-5-mercapto-2,4-dithiaphene Tylthio] -1,3-dithiane, 4,6-bis {4- (6-mercaptomethylthio) -1,3-ditianylthio} -1,3-dithiane, 4- {4- ( 6-mercaptomethylthio) -1,3-dithianylthio} -6- {4- (6-mercaptomethylthio) -1,3-ditianylthio} -1,3-dithiane, 3- { 2- (1,3-dithiethanyl)} methyl-7,9-bis (mercaptomethylthio) -1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9- { 2- (1,3-dithiethanyl)} methyl-3,5,13,15-tetrakis (mercaptomethylthio) -1,17-dimercapto-2,6,8,10,12,16 -Hexathiaheptadecane, 3- {2- (1,3-dithiethanyl)} methyl-7,9,13,15-tetrakis (mercaptomethylthio) -1,17-dimercapto-2, 4,6,10,12,16-hexathiaheptadecane, 3,7-bis {2- (1,3-dithiethanyl)} methyl-1,9-dimercapto-2,4,6,8 Tetrathianonane, 4- {3,4,8,9- Tetrakis (mercaptomethylthio) -11-mercapto-2,5,7,10-tetrathiaundecyl} -5-mercaptomethylthio-1,3-dithiolane, 4,5-bis {3, 4-bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio} -1,3-dithiolane, 4- {3,4-bis (mercaptomethylthio) -6-mer Capto-2,5-dithiahexylthio} -5-mercaptomethylthio-1,3-dithiolane, 4- {3-bis (mercaptomethylthio) methyl-5,6-bis (mercaptomethylthio ) -8-mercapto-2,4,7-trithiaoctyl} -5-mercaptomethylthio-1,3-dithiolane, 2- [bis {3,4-bis (mercaptomethylthio) -6 Mercapto-2,5-dithiahexylthio} methyl] -1,3-dithiethane, 2- {3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexyl Thio} mercaptomethylthiomethyl-1,3-dithiethane, 2- {3,4,8,9-tetrakis (mercaptomethylthio) -11-mercapto-2,5,7,10-tetratia Undecylthio} mercaptomethylthiomethyl-1,3-dithiethane, 2- {3-bis (mercaptomethylthio) methyl-5,6-bis (meth Lecaptomethylthio) -8-mercapto-2,4,7-trithiaoctyl} mercaptomethylthiomethyl-1,3-dithiethane, 4,5-bis [1- {2- (1,3- Dithiethanyl)}-3-mercapto-2-thiapropylthio] -1,3-dithiolane, 4- [1- {2- (1,3-dithiethanyl)}-3-mercapto-2 -Thiapropylthio] -5- {1,2-bis (mercaptomethylthio) -4-mercapto-3-thiabutylthio} -1,3-dithiolane, 2- [bis {4- (5- Mercaptomethylthio-1,3-dithioranyl) thio}] methyl-1,3-dithiethane, 4- {4- (5-mercaptomethylthio-1,3-dithioranyl) thio} -5 -[1- {2- (1,3-dithiethanyl)}-3-mercapto-2-thiapropylthio] -1,3-dithiolane and the like, but are not limited to these exemplary compounds. . Moreover, as long as it is a compound which has a dithio acetal or a dithio ketal skeleton, and has two or more mercapto groups, it may be a high molecular compound which does not have a specific repeating structure.
[48] Although there is no restriction | limiting in particular also about the polythiol compound which has an ortho trithio formate ester skeleton, For example, the compound represented by following General formula (2) is mentioned.
[49]
[50] In formula, R <^5> represents p-valent aliphatic residue, heterocyclic residue, and aromatic residue, R <^6> and R <^7> respectively independently represents monovalent aliphatic residue, heterocyclic residue, and aromatic residue, and R <^6> and R <^7> combine, It can form a ring. Provided that at least one of R ⁵ , R ^6, and R ⁷ has at least one mercapto group, and the number of mercapto groups in R ⁵ , R ^6, and R ⁷ is m5, m6, and m7, respectively, m5 + (m6 + m7) x p≥2. p represents an integer of 1 or more.
[51] R ⁵ is not particularly limited as long as it is p-valent organic residue derived from aliphatic, heterocyclic or aromatic, but is not limited to p-valent derived from linear aliphatic, cyclic aliphatic, heterocyclic or aromatic exemplified in R ¹ in formula (1). The organic residue or p-valent organic residue formed by removing a mercapto group from the above-mentioned thiol compound is preferable. R ⁶ and R ⁷ is also the aliphatic, heterocyclic, when the first organic residue monovalent derived from the aromatic There are no particular limitations on the expression (1), the mercapto group from the same, well-known thiol compounds and R ³ and R ⁴ in the The organic residue which removes is preferable, and can form a ring like R <^3> and R <^4> . There is no restriction | limiting in particular if p is an integer greater than or equal to 1, but the integer of 1-4 is preferable like n.
[52] As for the polythiol compound which has an ortho trithio formic acid ester skeleton represented by Formula (2), More specifically, for example, tris (mercaptomethylthio) methane, tris (mercaptoethylthio) methane, 1,1 , 5,5-tetrakis (mercaptomethylthio) -2,4-dithiapentane, bis (4,4-bis (mercaptomethylthio) -1,3-dithiabutyl) (mercaptomethylthio) Methane, tris (4,4-bis (mercaptomethylthio) -1,3-dithiabutyl) methane, 2,4,6-tris (mercaptomethylthio) -1,3,5-trithiacyclohexane , 2,4-bis (mercaptomethylthio) -1,3,5-trithiacyclohexane, 1,1,3,3-tetrakis (mercaptomethylthio) -2-thiapropane, bis (mercapto Methyl) methylthio-1,3,5-trithiacyclohexane, tris ((4-mercaptomethyl-2,5-dithiacyclohexyl-1-yl) methylthio) methane, 2,4-bis (mer Captomethylthio) -1,3-dithiacyclopentane, 2-mercaptoethylthio-4-mercaptomethyl-1,3-dithiacyclo Pentane, 2- (2,3-dimercaptopropylthio) -1,3-dithiacyclopentane, 4-mercaptomethyl-2- (2,3-dimercaptopropylthio) -1,3-di Thiacyclopentane, 4-mercaptomethyl-2- (1,3-dimercapto-2-propylthio) -1,3-dithiacyclopentane, tris (2,2-bis (mercaptomethylthio)- 1-thiaethyl) methane, tris (3,3-bis (mercaptomethylthio) -2-thiapropyl) methane, tris (4,4-bis (mercaptomethylthio) -3-thiabutyl) methane, 2 , 4,6-tris (3,3-bis (mercaptomethylthio) -2-thiapropyl) -1,3,5-trithiacyclohexane, tetrakis (3,3-bis (mercaptomethylthio) 2-thiapropyl) methane, these oligomers, etc. are mentioned, It is not limited only to these exemplary compounds. Moreover, if it has a trithio ortho formic acid ester frame | skeleton and two or more mercapto groups, the polymer which does not have a specific repeating structure may be sufficient.
[53] There is no restriction | limiting in particular also about the polythiol compound which has a tetrathio ortho carbonate ester frame | skeleton, For example, the compound represented by following General formula (3) is mentioned.
[54]
[55] Wherein, R ^8, R ^9, R ¹⁰ and R ¹¹ each independently represents an aliphatic moiety, a heterocyclic moiety, an aromatic moiety to form a ring, respectively, by combining the other of the groups. However, R ^8, R ^At least one of ⁹ , R ¹⁰ and R ¹¹ has one or more mercapto groups, and the number of mercapto groups in R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ is m8, m9, m10 and m11, respectively. In this case, m8 + m9 + m10 + m11
[56] R ⁸ , R ⁹ , R ^10, and R ¹¹ are not particularly limited as long as they are aliphatic residues, heterocyclic residues, or aromatic residues. Similarly to R ³ and R ^{4 in} formula (1), mercapto groups are removed from known thiol compounds. The organic residue which consists of these is preferable, and can form a ring like R3 and R4.
[57] If the polythiol compound which has a tetrathio ortho carbonate ester frame | skeleton represented by Formula (3) is illustrated more concretely, 3,3'-di (mercaptomethylthio) -1,5-dimercapto-2,4- Dithiapentane, 2,2'-di (mercaptomethylthio) -1,3-dithiacyclopentane, 2,7-di (mercaptomethyl) -1,4,5,9-tetrathiaspiro [4 , 4] nonane, 3,9-dimercapto-1,5,7,11-tetrathiaspiro [5,5] undecane, and the like, but are not limited to these exemplary compounds. Moreover, if it has tetrathio carbonate ester frame | skeleton and two or more mercapto groups, the polymer which does not have a specific repeating structure may be sufficient.
[58] The polythiol compound for use in the present invention is characterized by having a dithioacetal, dithioketal, orthotrithioformate ester or orthotetrathiocarbonate ester skeleton in the molecule, but mercapto for higher refractive index and heat resistance maintenance. It is preferable to have a methylthio group.
[59] Although the polymerizable composition of this invention contains the said polythiol compound, it is one of the characteristics, These polythiol compounds can be used individually and can be used in mixture of 2 or more types.
[60] Moreover, the other thiol compound can be used together as needed.
[61] For example, methanedithiol, ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,6-hexanedithiol, 1,2,3- Propanetriol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol , 2-methylcyclohexane-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, thiomalic acid bis (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptopropionate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercapto Propionate), 1,2-dimercaptopropylmethyl ether,
[62] 2,3-dimercaptopropylmethyl ether, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate) , Ethylene glycol bis (3-mercaptopropionate), trimethylolpropanebis (2-mercaptoacetate), trimethylolpropanebis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate ), Aliphatic polythiol compounds such as pentaerythritol tetrakis (3-mercaptopropionate), tetrakis (mercaptomethyl) methane,
[63] 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene , 1,4-bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1 , 2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2, 4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) Benzene, 1,3,5-tris (mercaptoethyl) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di (p-methoxyphenyl) propane-2,2- Aromatic polythiols such as dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane,
[64] 1,2-bis (mercaptoethylthio) benzene, 1,3-bis (mercaptoethylthio) benzene, 1,4-bis (mercaptoethylthio) benzene, 1,2,3-tris (mercaptomethyl Thio) benzene, 1,2,4-tris (mercaptomethylthio) benzene, 1,3,5-tris (mercaptomethylthio) benzene, 1,2,3-tris (mercaptoethylthio) benzene, 1 Aromatic polythiol compounds containing sulfur atoms in addition to mercapto groups such as 2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, and nucleoalkylates thereof ,
[65] Bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1 , 2-bis (mercaptoethylthio) ethane, 1,2-bis (3-mercaptopropyl) ethane, 1,3-bis (mercaptoethylthio) propane, 1,3-bis (3-mercaptopropyl Thio) propane, 1,2,3-tris (mercaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, 1,2-bis [(2-mercaptoethyl) thio ] -3-mercaptopropane, 4,8-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaoundecan, 4,7-dimercaptomethyl-1,11-mercapto -3,6,9-trithiaoundecan, 5,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundane, tetrakis (2-mercaptoethylthiomethyl) Methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, bis (1,3-dimercaptopropyl) sulfide, 2,5-di Lecapto-1,4-dithiane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, bis ( Mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide and the like, esters of thioglycolic acid and mercaptopropionic acid,
[66] Hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mer Captoacetate), hydroxymethyldisulfidebis (3-mercaptopropionate), hydroxyethyldisulfidebis (2-mercaptoacetate), hydroxyethyldisulfidebis (3-mercaptopropionate), Hydroxypropyl disulfide bis (2-mercaptoacetate), hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl etherbis (2-mercaptoacetate), 2-mercaptoethyl Etherbis (3-mercaptopropionate), 1,4-dithiane-2,5-diolbis (2-mercaptoacetate), 1,4-dithiane-2,5-diolbis (3-mercaptopropionate), thiodiglycol bis ( 2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), 4,4-thiodibutyl acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl Ester), dithiodipropionate bis (2-mercaptoethyl ester), 4,4-dithiodibutyl acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester) , Thiodipropionic acid bis (2,3-dimercaptopropyl ester), dithioglycolic acid bis (2,3-dimercaptopropyl ester), dithiodipropionic acid bis (2,3-dimercaptopropyl ester), etc. Aliphatic polythiol compounds containing sulfur atoms in addition to the mercapto group of
[67] Heterocyclic compounds containing sulfur atoms in addition to mercapto groups such as 3,4-thiophendithiol, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercaptoethanol, 3-mercapto- 1,2-propanediol, glycerindi (mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 3 , 4-dimercapto-2-propanol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, penta Erythritol tris (3-mercaptopropionate), pentaerythritol mono (3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycorate), dipentaerythritol Methacrylates such as pentacis (3-mercaptopropionate), hydroxymethyl-tris (mercaptoethylthiomethyl) methane, and 1-hydroxyethylthio-3-mercaptoethylthiobenzene The compound containing a hydroxyl group other than a lecapto group is mentioned. Moreover, the halogen substituent of these chlorine substituent and a bromine substituent can be used.
[68] The compound having two or more iso (thio) cyanato groups to be used in the present invention is not particularly limited, but specifically, hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane Diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecanetriisocyanate, 1,3,6-hexa Methylenetriisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, lysine diisocyanatomethyl ester, lysine triisocyanate, xyl Reylene diisocyanate, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, (alpha), (alpha), (alpha) ', (alpha)'-tetramethyl xylylene diisocyanate, bis (isocyanatobutyl) benzene, bis ( Iso Annatto methyl) naphthalene, bis (isocyanatomethyl phenyl) ether, bis (isocyanatoethyl) phthalate, 2,6-di (isocyanato-methyl) aliphatic polyisocyanate compounds such as furan,
[69] Isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, cyclohexanediisocyanate, methylcyclohexanediisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 4,4'-methylenebis (2-methyl Cyclohexyl isocyanate), 2,5-bis (isocyanatomethyl) bicyclo- [2,2,1] -heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2,2,1] -Heptane, 3,8-bis (isocyanatomethyl) tricyclodecane, 3,9-bis (isocyanatomethyl) tricyclodecane, 4,8-bis (isocyanatomethyl) tricyclodecane, 4, Alicyclic polyisocyanate compounds such as 9-bis (isocyanatomethyl) tricyclodecane,
[70] 1,2-diisocyanatobenzene, 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylenedi Isocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzenetriisocyanate, benzenetriisocyanate, biphenyldiisocyanate, toluidine diisocyanate, 4,4'-methylenebis (phenylisocyanate), 4,4'- Aromatic polyisocyanate compounds such as methylenebis (2-methylphenylisocyanate), bibenzyl-4,4'-diisocyanate, bis (isocyanatophenyl) ethylene,
[71] Bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfone, bis (Isocyanatomethyl) disulfide, bis (isocyanatoethyl) disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (Isocyanatoethylthio) ethane, bis (isocyanatomethylthio) ethane, 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane, 1,2,3-tris (isocyanato Methylthio) propane, 1,2,3-tris (isocyanatoethylthio) propane, 3,5-dithia-1,2,6,7-heptane tetraisocyanate, 2,6-diisocyanatomethyl-3 Such as, 5-dithia-1,7-heptane diisocyanate, 2,5-diisocyanate methylthiophene, 4-isocyanatoethylthio-2,6-dithia-1,8-octane diisocyanate Sulfur-containing aliphatic isocyanate compounds,
[72] Aromatic sulfide-based isocyanate compounds such as 2-isocyanatophenyl-4-isocyanatophenyl sulfide, bis (4-isocyanatophenyl) sulfide, and bis (4-isocyanatomethylphenyl) sulfide,
[73] Bis (4-isocyanatophenyl) disulfide, bis (2-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl- 6-isocyanatophenyl) disulfide, bis (4-methyl-5-isocyanatophenyl) disulfide, bis (3-methoxy-4-isocyanatophenyl) disulfide, bis (4-methoxy- Aromatic disulfide-based isocyanate compounds such as 3-isocyanatophenyl) disulfide,
[74] 2,5-diisocyanatotetrahydrothiophene, 2,5-diisocyanatomethyltetrahydrothiophene, 3,4-diisocyanatomethyltetrahydrothiophene, 2,5-diisocyanato-1,4- Dithiane, 2,5-diisocyanatomethyl-1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis (isocyanatomethyl) -1,3- Sulfur-containing alicyclic compounds such as dithiolane and 4,5-diisocyanatomethyl-2-methyl-1,3-dithiolane,
[75] Alicyclic isothiocyanate compounds such as 1,2-diisothiocyanatoethane and 1,6-diisothiocyanatohexane, cycloaliphatic isothiocyanate compounds such as cyclohexanediisothiocyanate, and 1,2 -Diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5-diisothiocyanato m-xylene, 4,4'-diisothiocyanatobiphenyl, 4,4'-methylenebis (phenylisothiocyanate), 4,4'-methylenebis (2-methylphenylisothiocyanate) , 4,4'-methylenebis (3-methylphenylisothiocyanate), 4,4'-isopropylidenebis (phenylisothiocyanate), 4,4'-diisothiocyanatobenzophenone, 4, Aromatic isothiocyanate compounds such as 4'-diisothiocyanato-3,3'-dimethylphenzophenone and bis (4-isothiocyanatophenyl) ether,
[76] Moreover, carbon, such as 1, 3- benzenedicarbonyl diisothiocyanate, 1, 4- benzenedicarbonyl diisothiocyanate, (2, 2-pyridine) -4, 4- dicarbonyl diisothiocyanate, etc. Sulfur-containing aliphatic isothiocia such as a carbonyl isothiocyanate compound, thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane), dithiobis (2-isothiocyanatoethane) Nate compound,
[77] 1-isothiocyanato-4-[(2-isothiocyanato) sulfonyl] benzene, thiobis (4-isothiocyanatobenzene), sulfonylbis (4-isothiocyanatobenzene), dithiobis Sulfur-containing aromatic isothiocyanate compounds such as (4-isothiocyanatobenzene), 2,5-diisothiocyanatothiophene, 2,5-diisothiocyanato-1,4-dithiane and the like Sulfur-containing alicyclic compounds,
[78] 1-isocyanato-6-isothiocyanatohexane, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3-iso Cyanato-1-isothiocyanatobenzene, 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, 4-isocyanatophenyl-4-isothiocyanatophenyl The compound which has isocyanato group and isothiocyanato group, such as sulfide and 2-isocyanatoethyl-2-isothiocyanatoethyl disulfide, etc. are mentioned.
[79] In addition, halogen substituents such as chlorine substituents and bromine substituents, alkyl substituents, alkoxy substituents, prepolymer-type modified compounds with nitro substituents and polyhydric alcohols, carbodiimide modified products, urea modified products, biuret modified products, dimerization or trimers The reaction product may also be used.
[80] These compounds can be used independently and can be used in mixture of 2 or more type.
[81] In addition, in the polymerizable composition of the present invention, in order to adjust optical properties such as the refractive index of the resin obtained mainly, or to adjust various physical properties such as impact resistance and specific gravity, or to adjust the viscosity and other handling properties of the polymerizable composition. In order to improve the monomer type and the resin, a resin modifier may be added.
[82] Further, when curing the polymerizable composition of the present invention, the chain extender, the crosslinking agent, the light stabilizer, the ultraviolet absorber, the antioxidant, the coloring agent, the bluing agent, and the oil-soluble agent are used as in the known molding method, depending on the purpose. Various substances such as dyes and fillers can be added.
[83] Moreover, in order to adjust to a desired reaction rate, a well-known reaction catalyst can be added suitably. As a catalyst used preferably, tin compounds, such as dibutyl tin dilaurate, dibutyl tin dichloride, and dimethyl tin dichloride, and amine compounds, such as a tertiary amine, can be used as a urethanation reaction catalyst, for example, It can be used independently and can be used together.
[84] Resin of this invention is obtained by casting polymerization normally. Specifically, various additives, such as a catalyst, a ultraviolet absorber, and an internal mold release agent, are previously mixed with the monomer to be used, and it is set as the mixed liquid. When adjusting a liquid mixture, it can adjust with the following means. ① The method of adding and mixing a thiol component after dissolving various additives in an isocyanate component. (2) A method of adding and mixing an isocyanate component after dissolving various additives in the thiol component. (3) A method of adding and dissolving various additives after mixing an isocyanate component and a thiol component. (4) A method in which various additives are dissolved in a high concentration in an isocyanate component or a thiol component in advance to prepare a master liquid, and this master liquid is added to a mixed liquid of an isocyanate component and a thiol component.
[85] If necessary, the mixed solution is degassed by a suitable method, and then injected into a mold composed of two glass plates, a tape, or a gasket, and polymerized. Although it does not specifically limit regarding injection | pouring, It is preferable that the viscosity of a monomer liquid mixture is 20-1000 mPa * s.
[86] The polymerization conditions at the time of polymerization can not be limited because the conditions vary greatly depending on the type of monomer used, the type of catalyst, the amount of addition thereof, the shape of the mold, and the like. , Over 1 to 100 hours.
[87] The resin of the present invention thus obtained is colorless and transparent, and has excellent optical and mechanical properties, and is suitable as optical element materials such as plastic lenses, prisms, optical fibers, information recording plates, filters, and light emitting diodes.
[88] In addition, in the lens using the optical resin of the present invention, the surface polishing is performed in order to improve such as antireflection, high hardness, abrasion resistance, chemical resistance, anti-fog, or fashion, as necessary. Physical or chemical treatments such as antistatic treatment, hard coat treatment, anti-reflective coat treatment, and dyeing treatment can be performed. In the dyeing, a hot bath in which disperse dyes are dispersed is usually used, but a dyeing bath in which a carrier represented by benzyl alcohol is added to improve the dyeing speed or dyeing concentration can be used.
[89] Hereinafter, an Example demonstrates this invention concretely.
[90] The physical property evaluation of resin obtained by superposition | polymerization was performed by the following method.
[91] Refractive index (ne), Abbe number (νe): It measured at 20 degreeC using the Pulfrich refractometer.
[92] Heat resistance: Tg was measured by TMA penetration method (load 50g, pin tip 0.5mm (phi), temperature rising 10 degreeC / min).
[93] Impact resistance: According to the US FDA standard, a dropping test was performed in which a steel ball weighing 16 g was dropped at a height of 127 cm to a lens having a center thickness of 1.0 mm. The crack which generate | occur | produced was made into △.
[94] Preparation Example 1
[95] In a 3-liter round-bottom flask equipped with agitating vanes, a thermometer and a luggage lot, 117.7 g (1.11 mol) of trimethyl orthoformate, 200.0 g (2.49 mol) of methanedithiol, 2 liters of toluene and 23.6 g (0.124 paratoluenesulfonic acid) mol) was added and stirred at 20 ° C for 43 hours. The reaction solution was washed several times with water. The organic layer was desolvated to remove toluene and low boiling point components, and then filtered through a 3 μm Teflon filter to obtain a mixture of 122.5 g of a polythiol compound (hereinafter referred to as polythiol compound A).
[96] Three peaks were observed in the peak area ratio of 18:29:53 by GPC measurement of the polythiol compound A (column: TOSOH CORPORATION "G1000HXL" 7.8 mm x 300 mm, eluent: THF). Of these three components, the two components on the low molecular weight side were separately collected by liquid chromatography and analyzed, and as a result, tris (mercaptomethylthio) methane (hereinafter referred to as TMMTM), and 1,1,5,5-tetrakis, respectively It was found that it was (mercaptomethylthio) -2,4-dithiapentane (referred to as TMMTDTP). The analysis results of these two compounds are shown below. Based on these two components, the molecular weight of the remaining one component was calculated from the results of GPC analysis, and the result was a number average molecular weight of 585 and a weight average molecular weight of 589. It was found that the captomethylthio) -1,3-dithiabutyl) (mercaptomethylthio) methane (molecular weight 591).
[97] It was 10.6 meq / g when the equivalent number of mercapto groups per unit mass of polythiol compound A (henceforth SHV) was computed from the peak area ratio of GPC.
[98]
[99]
[100] Example 1
[101] 47.2 g of xylylene diisocyanate is 10 mg of dibutyltin dichloride as a catalyst, 100 mg of `` Zelec UN '' (trade name, manufactured by stepan, an acidic alkyl phosphate ester) as an internal mold release agent, and `` Biosorb 583 '' as a ultraviolet absorber (trade name, Kyodo 50 mg of Yakuhinsha Co., Ltd. was previously dissolved to prepare a mixed solution. Subsequently, 52.8 g of the polythiol compound A obtained in the manufacture example 1 were added, it mixed well, and it was set as the monomer mixture. At this time, the molar ratio of the mercapto group and the isocyanato group in the monomer mixture was SH / NCO = 1.12. After degassing this monomer mixture at 0.6 kPa for 1 hour, a part of it was injected into a lens mold, and gradually heated up at 40 degreeC, it heated to 120 degreeC, and hardened over 21 hours. After cooling, the glass mold was released to take out the lens. The obtained lens was colorless and transparent, and the lens was not blurred even though light was transmitted through the slide projector in the dark room. The optical properties were 1.704 and Abbe's number (v) of refractive index ne. The heat resistance was good at a Tg point of 94.3 ° C. Impact resistance was (circle).
[102] Preparation Example 2
[103] To 1,1,3,3-tetramethoxypropane 164.2 g (1 mol) in a flask with a 2-liter bottomed coke equipped with a stirring vane, a thermometer, a distillation column, and a capillary for introducing nitrogen. 488.8 g (4 mol) of acetyl mercaptomethyl mercaptan and 7.6 g (0.04 mol) of paratoluenesulfonic acid were added, and it heated to 40 degreeC, stirring, maintaining the vacuum degree of 1 kPa or less. Heating was continued for about 18 hours until the distillation of methanol stopped. After cooling, the vacuum was released, a condenser was installed instead of a distillation column, and 400 ml of methanol, 400 ml of chloroform, and 200 ml of 36% hydrochloric acid were added thereto, followed by heating to 60 DEG C. It carried out and produced | generated the 1,1,3,3- tetrakis (mercaptomethylthio) propane (henceforth a polythiol compound B) which is a target compound.
[104] An appropriate amount of water and chloroform were added to separate and the chloroform layer was washed several times with water. The solvent was removed to remove chloroform and the low boiling point component, and then filtered through a 3 µm Teflon filter to obtain 340.0 g of a polythiol compound B. By LC analysis of the polythiol compound B, two components other than the polythiol compound B were detected (9.8% and 9.8%, respectively, by chromatogram area ratio). These components were purified by preparative LC, and analyzed as a result. 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2- (2,2-bis (mercaptomethylthio) ethyl)- 1,3-dithiethane. The analysis results are shown below.
[105] Moreover, when SHV of polythiol compound B (containing the said by-product two components) was computed using the chromatogram area ratio of LC, it was 10.5 meq / g.
[106] Iii) 1,1,3,3-tetrakis (mercaptomethylthio) propane
[107]
[108] Iii) 4,6-bis (mercaptomethylthio) -1,3-dithiane
[109]
[110] Viii) 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-diethane
[111]
[112] Example 2
[113] 45.6 g of xylylene diisocyanate, 30 mg of dibutyltin dichloride as a catalyst, 150 mg of `` Zelec UN '' (trade name, manufactured by stepan, acidic alkyl phosphate) as an internal mold release agent, `` Biosorb 583 '' (trade name, Kyodo-do) 50 mg of Yakuhinshasha) was melt | dissolved previously, and it was set as the liquid mixture. Next, 54.4 g of the polythiol compound B obtained in the manufacture example 2 was added, it mixed well, and it was set as the monomer mixture. At this time, the molar ratio of the mercapto group and the isocyanato group in the monomer mixture was SH / NCO = 1.18. After degassing this monomer mixture at 0.6 kPa for 1 hour, a part of it was injected into a lens mold, and gradually heated up at 40 degreeC, it heated to 130 degreeC, and hardened over 20 hours. After cooling, the glass mold was released to take out the lens. The obtained lens was colorless and transparent, and the lens was not blurred even though light was transmitted through the slide projector in the dark room. The optical properties of the refractive index ne were 1.693 and the Abbe number ve was 30. The heat resistance was good at a Tg point of 99.5 ° C. Impact resistance was (circle).
[114] Preparation Example 3
[115] To 1,1,3,3-tetramethoxypropane 164.2 g (1 mol) in a flask with a 2-liter bottomed coke equipped with a stirring vane, a thermometer, a distillation column, and a capillary for introducing nitrogen. 488.8 g (4 mol) of acetyl mercaptomethyl mercaptan is added and cooled to 5 ° C. Paratoluenesulfonic acid 7.6g (0.04mol) was added here, and it heated up to 50 degreeC over 4 hours, stirring and maintaining the vacuum degree of 2.67kPa. After heating up at 50 degreeC, heating was continued for about 5 hours until the distillation discharge | release of methanol stopped. After cooling, the vacuum was released, and a condenser was installed instead of a distillation column. Then, 176.9 g of methanol, 353.7 g of toluene, and 30.4 g (0.16 mol) of paratoluene sulfonic acid were added, heated to 60 ° C., and alcohol decomposition was carried out. , Polythiol compound B was produced.
[116] The toluene layer was washed several times with water using an appropriate amount of water. The solvent was removed to remove toluene and the low boiling point component, and then filtered through a 1 µm Teflon filter to obtain 340.0 g of a polythiol compound B. In the same manner as in Production Example 2, two components were detected by LC analysis of the polythiol compound B except for the polythiol compound B. These two components were the same as that of the manufacture example 2.
[117] Moreover, it was 9.8 meq / g when the SHV of Polythiol compound B (containing the said by-product two components) was measured.
[118] Example 3
[119] 44.3 g of xylylene diisocyanate is 20 mg of dibutyltin dichloride as a catalyst, 100 mg of "Zelec UN" (trade name, manufactured by stepan, acidic alkyl phosphate ester) as an internal mold release agent, and "Biosorb 583" as a ultraviolet absorber (trade name, Kyodo 50 mg of Yakuhinshasha) was melt | dissolved previously, and it was set as the liquid mixture. Next, 55.7 g of the polythiol compound B obtained in the manufacture example 3 was added, it mixed well, and it was set as the monomer mixture. At this time, the molar ratio of the mercapto group and the isocyanato group in the monomer mixture was SH / NCO = 1.16. After degassing this monomer mixture at 0.6 kPa for 1 hour, it filtered by 1 micrometer Teflon filter, a part was injected into the lens mold, it heated up slowly at 40 degreeC, it heated to 130 degreeC, and hardened over 20 hours. After cooling, the glass mold was released to take out the lens. The obtained lens was colorless and transparent, and the lens was not blurred even though light was transmitted through the slide projector in the dark room. The optical properties showed that the refractive index ne was 1.695 and the Abbe number ve was 30. The heat resistance was good at the Tg point of 100.1 ° C. Impact resistance was (circle).
[120] Preparation Example 4
[121] The same operation as in Production Example 3 was carried out except that the vacuum degree was maintained at 4.00 kPa.
[122] It was 9.5 meq / g when the SHV of the obtained polythiol compound B was measured.
[123] Example 4
[124] The same operation as in Example 3 was carried out except that the polythiol compound B obtained in Production Example 4 was used. At this time, the molar ratio of the mercapto group and the isocyanato group in the monomer mixture was SH / NCO = 1.13. The obtained lens was colorless and transparent, and the lens was not blurred even though light was transmitted through the slide projector in the dark room. The optical properties were 1.696 and Abbe's number ( E) of the refractive index ne. The heat resistance was good at a Tg point of 100.0 ° C. Impact resistance was (circle).
[125] Preparation Example 5
[126] The same operation as in Production Example 3 was carried out except that the vacuum degree was maintained at 5.33 kPa.
[127] It was 9.3 meq / g when the SHV of the obtained polythiol compound B was measured.
[128] Example 5
[129] The same operation as in Example 3 was carried out except that the polythiol compound B obtained in Production Example 5 was used. At this time, the molar ratio of the mercapto group and the isocyanato group in the monomer mixture was SH / NCO = 1.09. The obtained lens was colorless and transparent, and the lens was not blurred even though light was transmitted through the slide projector in the dark room. The optical properties were 1.696 and Abbe's number ( E) of the refractive index ne. The heat resistance was good at the Tg point of 103.1 占 폚. Impact resistance was (circle).
[130] Comparative Example 1
[131] 49.8 g of xylylene diisocyanate and 50.2 g of polythiol compound A were polymerized in the same manner as in Example 1 to obtain a lens. Moreover, the molar ratio of the mercapto group and the isocyanato group in the monomer mixture was SH / NCO = 1.01. The optical properties showed that the refractive index ne was 1.700 and the Abbe's number (νe) was 30. The heat resistance was Tg point 96.0 degreeC. Impact resistance was (circle).
[132] Comparative Example 2
[133] Although 24.9 g of xylylene diisocyanate and 75.1 g of polythiol compound A were polymerized in the same manner as in Example 1, the obtained resin was rubbery at room temperature, and a resin having good heat resistance was not obtained. Moreover, the molar ratio of the mercapto group and the isocyanato group in a monomer mixture was SH / NCO = 3.004.
[134] Comparative Example 3
[135] It polymerized similarly to Example 2 using 50.0 g of xylylene diisocyanate and 50.0 g of polythiol compounds B obtained by the manufacture example 2, and the lens was obtained. Moreover, the molar ratio of the mercapto group and the isocyanato group in the monomer mixture at this time was SH / NCO = 0.99. The optical properties showed that the refractive index ne was 1.688 and the Abbe number ve was 30. Heat resistance was Tg point 106.0 degreeC. Impact resistance was (circle).
[136] Comparative Example 4
[137] Although 24.7 g of xylylene diisocyanate and 75.3 g of polythiol compound B obtained in Production Example 2 were polymerized in the same manner as in Example 2, the obtained resin was rubbery at room temperature, and a resin having good heat resistance was not obtained. Moreover, the molar ratio of the mercapto group and the isocyanato group in a monomer mixture was SH / NCO = 3.01.
[138] Comparative Example 5
[139] 48.0 g of xylylene diisocyanate and 52.0 g of polythiol compound B obtained in Production Example 3 were polymerized in the same manner as in Example 2 to obtain a lens. Moreover, the molar ratio of the mercapto group and the isocyanato group in the monomer mixture at this time was SH / NCO = 1.00. The optical properties were 1.690 and Abbe's number (νe) of refractive index ne. Heat resistance was Tg point 106.3 degreeC. Impact resistance was (circle).
[140] Comparative Example 6
[141] 47.3 g of xylylene diisocyanate and 52.7 g of polythiol compound B obtained in Production Example 4 were used to polymerize in the same manner as in Example 3 to obtain a lens. Moreover, the molar ratio of the mercapto group and the isocyanato group in the monomer mixture at this time was SH / NCO = 1.00. The optical properties were 1.690 and Abbe's number (νe) of refractive index ne. Heat resistance was Tg point 106.3 degreeC. Impact resistance was (circle).
[142] Comparative Example 7
[143] 48.0 g of xylylene diisocyanate and 52.0 g of polythiol compound B obtained in Production Example 4 were polymerized in the same manner as in Example 4 to obtain a lens. Moreover, the molar ratio of the mercapto group and the isocyanato group in the monomer mixture at this time was SH / NCO = 1.00. The optical properties were 1.690 and Abbe's number (νe) of refractive index ne. Heat resistance was Tg point 109.2 degreeC. Impact resistance was (circle).
[144] Comparative Example 8
[145] 10 mg of dibutyltin dichloride as a catalyst to 52.0 g of xylylene diisocyanate, 100 mg of `` Zelec UN '' (trade name, stepan, acidic alkyl phosphate) as an internal mold release agent, `` Biosorb 583 '' (trade name, Kyodoya) 50 mg) was previously dissolved to prepare a mixed solution. Next, 48.0 g of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (hereinafter referred to as polythiol compound C) was added and mixed well to obtain a monomer mixture. At this time, the molar ratio of the mercapto group and the isocyanato group in the monomer mixture was SH / NCO = 1.00. After degassing this monomer mixture at 0.6 kPa for 1 hour, a part of it was injected into a lens mold, and gradually heated up at 40 degreeC, it heated to 120 degreeC, and hardened over 20 hours. After cooling, the glass mold was released to take out the lens. The obtained lens was colorless and transparent, and the lens was not blurred even though light was transmitted through the slide projector in the dark room. The optical properties were 1.660 and Abbe's number (νe) of refractive index ne. The heat resistance was Tg point 85.0 degreeC. Impact resistance was (circle).
[146] Comparative Example 9
[147] 48.5 g of xylylene diisocyanate and 51.5 g of polythiol compound C were used to polymerize in the same manner as in Comparative Example 5 to obtain a lens. Moreover, the molar ratio of the mercapto group and the isocyanato group in the monomer mixture at this time was SH / NCO = 1.15. The obtained lens was colorless and transparent, and the lens was not blurred even though light was transmitted through the slide projector in the dark room. The optical properties of the refractive index ne were 1.663 and the Abbe number ve was 32. The heat resistance was Tg point 62.1 degreeC. Impact resistance was (circle).
[148] Comparative Example 10
[149] 10 mg of dibutyltin dichloride as a catalyst to 50.7 g of xylylene diisocyanate, 100 mg of `` Zelec UN '' (trade name, manufactured by stepan, acidic alkyl phosphate ester) as an internal mold release agent, `` Biosorb 583 '' (trade name, Kyodo-do) 50 mg of Yakuhinshasha) was melt | dissolved previously, and it was set as the liquid mixture. Subsequently, 49.3 g of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan (hereinafter referred to as polythiol compound D) are added and mixed well, and the monomer mixture It was set as. The molar ratio of mercapto group and isocyanato group in the monomer mixture was SH / NCO = 1.00. After degassing this monomer mixture at 0.6 kPa for 1 hour, a part of it was injected into a lens mold, and gradually heated up at 40 degreeC, it heated to 120 degreeC, and hardened over 20 hours. After cooling, the glass mold was released to take out the lens. The obtained lens was colorless and transparent, and the lens was not blurred even though light was transmitted through the slide projector in the dark room. The optical properties were 1.667 and Abbe's number (ve) of refractive index (ne). Heat resistance was Tg point 100.2 degreeC. Impact resistance was (circle).
[150] Comparative Example 11
[151] 46.1 g of xylylene diisocyanate and 53.9 g of a polythiol compound D were polymerized in the same manner as in Comparative Example 7 to obtain a lens. Moreover, the molar ratio of the mercapto group and the isocyanato group in the monomer mixture at this time was SH / NCO = 1.20. The obtained lens was colorless and transparent, and the lens was not blurred even though light was transmitted through the slide projector in the dark room. The optical properties were 1.670 and Abbe's number ( E) of the refractive index ne. The heat resistance was Tg point 82.1 degreeC. Impact resistance was (circle).
[152] The above result was put together in Table 1. Δne and ΔTg in the table indicate the refractive index (ne) and heat resistance (Tg) of the resin obtained when the molar ratio (SH / NCO) of the mercapto group and the isocyanato group in the monomer mixture is larger than 1.01 and 1.0 or less, respectively. The difference is shown. Therefore, the larger the value of Δne / ΔTg, the lower the heat resistance is suppressed, and the higher the refractive index. In the resin obtained from the polymerizable composition containing the polythiol of the present invention, Δne / ΔTg is larger than the comparative example using a conventional polythiol, that is, the refractive index is significantly improved, while the heat resistance decrease is small, The impact resistance was also maintained. However, in Comparative Examples 5, 6, 7 and 8, when the molar ratio of the mercapto group and the isocyanato group in the polymerizable composition exceeded 1.0, the heat resistance significantly decreased.
[153] Moreover, about the heat resistance of resin, since the heat resistance of resin shown in the comparative example 5 which is the typical thiourethane type optical resin generally widely spread was 85.0 degreeC, if it has more than this heat resistance, it can fully endure practical use. Therefore, although the heat resistance of resin in an Example can be said to be a practically practical range, heat resistance is not enough in resin of the comparative examples 6 and 8. In addition, as shown in Comparative Examples 2 and 4, when the ratio of the mercapto group and the isocyanato group exceeds 3.0, it becomes a rubbery resin, and a resin having good heat resistance cannot be obtained. In the above Example, although the compound which has isocyanato group was demonstrated, the same result is obtained even if the compound which has isothiocyanato group is used.
[154] Thiol SH / NCO molar ratioRefractive index (ne)Heat resistance (℃)Impact resistanceΔne / Tg (× 10 ^-3 ) Polythiol Compound AExample 11.121.70494.3○2.11 Comparative Example 11.001.70096.2○ Polythiol Compound BExample 21.181.69399.5○0.77 Comparative Example 30.991.688106.0○ Polythiol Compound BExample 31.161.695100.1○0.85 Comparative Example 51.001.690106.0○ Polythiol Compound BExample 41.131.696100.0○0.95 Comparative Example 61.001.690106.3○ Polythiol Compound BExample 51.091.696103.1○0.98 Comparative Example 71.001.690109.2○ Polythiol Compound CComparative Example 91.151.66362.1○0.13 Comparative Example 81.001.66085.0○ Polythiol Compound CComparative Example 111.201.67082.1○0.17 Comparative Example 101.001.667100.1○
[155] According to the present invention, high refractive index of the resin can be easily maintained while maintaining heat resistance and impact resistance.

权利要求:
Claims (15)
[1" claim-type="Currently amended] A polythiol compound having a dithioacetal, dithioketal, orthotrithioformate ester or orthotetrathiocarbonate ester skeleton, having two or more mercapto groups, and a compound having two or more iso (thio) cyanato groups As a composition to contain, the polymeric composition for high refractive index resins whose molar ratio of a mercapto group and an iso (thio) cyanato group is more than 1.0 and 3.0 or less.
[2" claim-type="Currently amended] The polymerizable composition according to claim 1, wherein the polythiol compound has a mercaptomethylthio group.
[3" claim-type="Currently amended] Polymeric composition of Claim 1 or 2 containing the polythiol compound which has a dithioacetal or a dithio ketal skeleton represented by following General formula (1):

(Wherein R ¹ is an n-valent aliphatic residue, a heterocyclic residue, an aromatic residue, R ² is a hydrogen atom or a monovalent aliphatic residue, a heterocyclic residue, an aromatic residue, and R ³ and R ⁴ are each independently monovalent An aliphatic moiety, a heterocyclic moiety, or an aromatic moiety, wherein R ³ and R ⁴ may combine to form a ring, and when n is 2 or more, may combine with R ³ or R ⁴ in other parentheses to form a ring; Provided that at least one of R ¹ , R ² , R ^3, and R ⁴ has at least one mercapto group, and that the number of mercapto groups in R ¹ , R ² , R ^3, and R ⁴ has m1, When m2, m3 and m4 are set, m1 + (m2 + m3 + m4) × n ≧ 2; n represents an integer of 1 or more.).
[4" claim-type="Currently amended] The polymerizable composition according to claim 3, wherein R ² in General Formula (1) is a hydrogen atom.
[5" claim-type="Currently amended] The polythiol compound having a dithioacetal skeleton is selected from the group consisting of 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio). ) Ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane and 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-diethane Polymeric composition which is the above polythiol compound.
[6" claim-type="Currently amended] Polymeric composition of Claim 1 or 2 containing the polythiol compound which has an ortho trithio formate ester frame | skeleton represented by following General formula (2):

(Wherein R ⁵ represents p-valent aliphatic residue, heterocyclic residue, aromatic residue, R ⁶ and R ⁷ each independently represents monovalent aliphatic residue, heterocyclic residue, aromatic residue, and R ⁶ and R ⁷ are bonded) Wherein at least one of R ⁵ , R ^6, and R ⁷ has at least one mercapto group, and m 5 represents the number of mercapto groups each of R ⁵ , R ^6, and R ⁷ has; , m6 and m7, m5 + (m6 + m7) × p ≧ 2; p represents an integer of 1 or more.).
[7" claim-type="Currently amended] The polymerizable composition according to claim 6, wherein R ⁶ and R ⁷ in General Formula (2) are mercaptomethyl groups.
[8" claim-type="Currently amended] The polythiol compound represented by the general formula (2) is tris (mercaptomethylthio) methane, 1,1,5,5-tetrakis (mercaptomethylthio) -2,4-diti A polymerizable composition which is at least one polythiol compound selected from apentane and bis (4,4-bis (mercaptomethylthio) -1,3-dithiabutyl) (mercaptomethylthio) methane.
[9" claim-type="Currently amended] Polymeric composition of Claim 1 or 2 containing the polythiol compound which has the ortho-tetrathio carbonate ester frame | skeleton represented by following General formula (3):

(Wherein R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent an aliphatic moiety, a heterocyclic moiety, an aromatic moiety, and each may combine with another group to form a ring; provided that R ⁸ , At least one of R ⁹ , R ¹⁰ and R ¹¹ has at least one mercapto group, and the number of mercapto groups in R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ is m8, m9, m10 and m11, respectively. M8 + m9 + m10 + m11 ≥ 2).
[10" claim-type="Currently amended] The manufacturing method of resin formed by hardening | curing the polymeric composition of any one of Claims 1-9.
[11" claim-type="Currently amended] Resin formed by hardening | curing the polymeric composition of any one of Claims 1-9.
[12" claim-type="Currently amended] The optical element which consists of resin of Claim 11.
[13" claim-type="Currently amended] A lens comprising the optical element according to claim 12.
[14" claim-type="Currently amended] 4,6-bis (mercaptomethylthio) -1,3-dithiane.
[15" claim-type="Currently amended] 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithiethane.

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同族专利:

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公开号 | 公开日

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TW200304920A|2003-10-16|

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CN1578798A|2005-02-09|

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AU2003235176B2|2007-11-01|

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EP1505094B1|2014-01-22|

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CN100343299C|2007-10-17|

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EP1505094A4|2007-03-21|

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US20070149822A1|2007-06-28|

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WO2003089488A1|2003-10-30|

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TW593436B|2004-06-21|

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AU2003235176A1|2003-11-03|

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US7396900B2|2008-07-08|

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EP1505094A1|2005-02-09|

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US20050131203A1|2005-06-16|

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KR100616795B1|2006-08-28|

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US7244808B2|2007-07-17|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2002-04-19|Priority to JP2002117531

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2002-04-19|Priority to JPJP-P-2002-00117531

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2003-04-16|Application filed by 미쓰이 가가쿠 가부시키가이샤

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2003-04-16|Priority to PCT/JP2003/004816

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2004-06-23|Publication of KR20040053258A

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2006-08-28|Application granted

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2006-08-28|Publication of KR100616795B1

优先权:

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申请号 | 申请日 | 专利标题

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JP2002117531|2002-04-19|

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JPJP-P-2002-00117531|2002-04-19|

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PCT/JP2003/004816|WO2003089488A1|2002-04-19|2003-04-16|Thiourethane-based optical material|